Amidelike derivatives and process of making the same



Patented Mar. 18, 1941 xgoit' #953 Reference PATENT OFFICE AMIDELIKE DERIVATIVES AND PROCESS OF MAKING THE SAME Charles Graenacher, Riehen, Franz Ackermann, Binningen, and Heinrich Bruengger, Basel, Switzerland, assignors to the firm of Society of Chemical Industry in Basle, Basel, Switzerland No Drawing. Application November 8, 1937, Se-

rial No. 173,528. In Switzerland November 11,

14 Claims.

This invention relates to the manufacture of new condensation products by treating compounds which are free from hydroxyl groups and obtainable by reacting primary amines with carboxylic acid chlorides or such other compounds containing mobile halogen atoms, for example cyanuric chloride, trichloropyrimidine, methyldichloropyrimidine, 2:6-dichloroquinazoline, monochloro- 'phthalazine and the like, which consist of a sixmembered heterocyclic ring consisting itself of nitrogen atoms and carbon atoms and which contain at least once the atom grouping with an acylating agent containing besides the group which determines the acylation at least one substituent which lends, if desired after suitable conversion, to the new product solubility or increased solubility.

Compounds which are free from hydroxyl groups and obtainable as indicated above are, for example, the products of the general formula wherein n stands for a whole number which is greater than one and smaller than 4, R1 stands for the residue of a carboxylic acid or for the radical of a heterocyclic six-membered system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 2 and not more than 4 are carbon atoms and at least two and not more than 3 are nitrogen atoms, not more than two nitrogen atoms being linked with each other, which heterocyclic six-membered ring contains at least twice and not more than three times the atom grouping stands for the radical of a primary amine.

The compounds corresponding to the above explained general formulas may or may not have dyestufi character; further they may belong to various classes of. compounds of the organic chemistry. Thus they may be aliphatic-aromatic, aliphatic-cyclo-aliphatic, ar omatic-heterocyclic, heterocyclic-cycle-aliphatic, and the like.

Acylating agents which contain besides the. acylating groups a substituent which enhances the solubility of the new condensation product, particularly in water, are for example halides or anhydrides of at least dibasic aliphatic, hydroaromatic or aromatic acids which contain sulfogroups or carboxyl groups or both, or halides or anhydrides of acids which contain alkylaminogroups besides the acid residues, so that after acylation the acyl residue still contains groups which can be converted into alkali metal compounds or quaternary ammonium compounds. The acylation is conducted in presence of a tertiary base, for instance pyridine, acylating agents may therefore be used of which the non-acylating substituent enters into reaction with the tertiary base and thereby enhances the solubility of the parent material. As examples of the acylating agents defined in this paragraph there may be named halides of sulfo-carboxylic acids in which both the sulfo-group and the carboxyl group is in the form of a halide; also those in which only the sulfo-group or the carboxyl group is present in the form of halide such as the halide of sulfo-benzoic acids, of sulfonaphthoic acids, of sulfoacetic acid or the like; also the 4-dialkylamino-l-benzoyl halides, the 4-halogenalkyl-lbenzoyl halides and the like (compare in this respect the statements of applications Serial No. 92,244 oi. July 23, 1936, and No. 92,245 of July 23, 1936).

The acylation process may be conducted, for example by heating a parent material with the and acylatlng agent in presence oi. a tertiary base.

oearcn m It is especially recommended, however, that the operation should be conducted in the presence of pyridine. Dimethylaniline may also be used.

By the process of condensation sparingly soluble to insoluble parent materials may be converted into products which are more easily soluble. These soluble or freel soluble compounds may then be used as such or be regenerated to the insoluble to sparingly soluble parent material by treatment with a saponifying agent, for instance dilute caustic alkali or dilute acid. The regenerated material may in this manner be fixed fast upon or in a substratum, for example on or in-a fiber or an artificial mass. In this manner various effects such as matting or coloring may be produced.

When aliphatic bodies are selected for the condensation, for example an amide of a fatty acid of high molecular weight, such as stearic acid, and an aliphatic primary amine, for instance mono-ethylamine, there are obtained according to the choice of the acylating agent assistants having cation activity or anion activity. Products having a similar action are further obtained if aliphatic-aromatic or aliphatic-heterocyclic or aliphatic-cycloaliphatic products, such as the amides from higher fatty acids, for example oleic acid or cocoanut oil fatt acid and aniline 0r cyclohexylamine, are subjected to the new reaction.

Condensation products from sparingly soluble colorless aromatic compounds, for instance the condensation product from 1 mol cyanuric chloride and 3 mols of a primary uncolored aromatic base, may be used for example as a matting agent.

Especially valuable, however, are parent materials which have at the same time a more or less strongly pronounced dyestuff character and contain the aforesaid atomic grouping, especially dyestuffs which are sparingly soluble or insoluble. These dyestuffs may belong to various series, for example the azo-dyestufl series or the vat dyestuff series, for instance the anthraquinone series. They may, however, belong to other series, for example those of the nitro-, azineor thiazine dyestuffs. Such dyestuffs may be also metallic compounds; thus as compounds which contain no hydroxyl groups there may also be considered compounds which contain masked hydroxyl groups, as is the case, for example, in the chromium compounds of the mordant dyestuffs. Among 'such dyestuffs those are of especial value which are of such a composition that they or their soluble derivatives have an amnity for vegetable fibers.

The condensation products obtainable from parent materials having dyestuif characteristics and capable of reversion by action of a saponifying agent, for instance an alkali, to the sparingly soluble dyestufi may be used, for example, for producing fast dyeings by the process of Patent No. 2,095,600. If the acyl residue which lends solubility is sufiiciently stable towards saponifying agents, insoluble dyestuffs may be converted into those which may be used by'the methods usual for dyeing with water-soluble dyestuffs.

The new process consists therefore in causing acylating agents containing besides the group effecting the acylation at least one group which reacts with the tertiary amine with formation of salts, to act in the presence of a tertiary base on mpounds which are free from hydroxyl groups and correspond to the above explained general formulas R|i IR2 H and The new products therefore correspond to the general formulas R1-TR2 R:

in which n stands for a whole number which is and .greater'than one'and smaller than 4,

stands for the divalent radical of an amine which is substituted twice at the nitrogen atom, R1 stands for the radical of an organic carboxylic acid or the radical of a heterocyclic six-membered ring system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic six-membered ring contains at least twice and at the most three times the atom grouping (I3=N IIIR2 R:

and R3 stands for an acyl radical containing at least one salt forming group selected from the group consisting of carboxyl groups, sulfonic groups and quaternary ammonium roups. They may be used for improving or dyeing various materials, for example vegetable and animal fibers, such as wool, silk, leather or artificial fibers, for instance fibers from regenerated cellulose or cellulose derivatives, and natural or artificial masses.

A preferred method of Working of the new process consists in treating dyestuffs of the azo or anthraquinone series corresponding to the above explained formula acid amide-like derivatives of the general for-' and 260. CHEMISTRY, CARBON 'cowouwos,

in which n stands for a whole number which is greater than one and smaller than 4,

stands for the divalent radical of an amine, said amine being an amino-azoor an amino-anthraquinone-dyestuff which is free from hydroxyl groups and carboxyl groups, R1 stands for the radical of a heterocyclic slx-membered ring system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic sixmembered ring contains at least twice and at the most three times the atom grouping C=N +41, R:

and R: corresponds in the free state to (:1: standing for $0311 and y for a member of the group consisting of H and 303K) which products are water-soluble powders which, when treated with mild saponifying agents, regenerate the amdyestufls or anthraquinone dyestuffs free from radicals R3, hydroxyl, carboxyl and sulfonic groups and corresponding to the formula n, R1 and having, apart from the foregoing statement, the meaning given at the beginning of this paragraph.

The following examples illustrate the invention without however limiting the same, the parts being by weight:

Example 1 3 parts of stearoylmethylamide, 4.4 parts of benzoic acid 3-sulfochloride and 30 parts of pyridine are heated together for one hour at -90 C. until a sample dissolves clearly in water. After removal of nearly all the pyridine in a vacuum, the bright liquid residue is taken up with 400 parts of water and then neutralized with dilute sodium carbonate solution, and the product of reaction is salted out with sodium chloride. It is filtered and dried. The nearly white product obtained in this manner in solid form dissolves in water to a colorless clear solution with formation of'a strong foam. It corresponds probably in the free state to one of the formulas By mixing the solution with aqueous alkali the product is split with separation or the insoluble parent material.

A like product is obtained by substituting lauroyl anilide or the lauroylcyclohexvlamide for the stearoylmethylamide.

In like manner benzoic acid ethylamide may be converted into a soluble derivative.

Example 2 To 17.7 parts of the condensation product from 1 mol of cyanuric chloride and 3 mols aniline in parts of pyridine are added 44 parts of benzoic acid meta-sulfo chloride and the temperature is allowed to rise to 80 C. The mixture is then stirred at 80 C. until a sample dissolves clearly in water, which happens after about 30 minutes.

After working up the product as described in Example 1 there is obtained a bright powder soluble in water and capable of being split by alkalies. The new product corresponds probably to one of the two following formulas S O;Na S 0iNa and in which at least two of the hydrogen atoms linked to the nitrogen atoms are replaced by the atom grouping In a similar manner there is obtained from 2:4- dinitrodlphenylamine and benzoic acid-meta-disulfochloride a water-soluble product of the formula the aqueous solution of which regenerates the diificultly soluble nitro dyestuff on addition of alkalies.

Example 3 1.65 parts of benzoylaminoazotoluene, 2.3 parts of benzoic acid 3:5-disuli'ochloride and 30 parts of pyridine are heated together for 3 hours at 110-115 C., whereby the insoluble parent material becomes soluble in water. The pyridine is distilled as far as possible in a vacuum. The residue is taken up with 100 parts of methyl alcohol, the solution is filtered from a little insoluble substance and the filtrate is evaporated. There is thus obtained a dark viscid product corresponding probably to one of the two formulas SIOzNB.

C O (EH3 (EH: S OaNa and S OaNii O I If OC CH3 OH:

| I SOaNa 3 G Q which dissolvesclearlyin cold water. When the aqueous solution is heated and dilute sodium carbonate solution is added thereto there is a rapid decomposition, the decomposition product proving to be benzoylaminoazotoluene (melting point 178C.)

A similar product is obtained if instead of the benzoylaminoazotoluene there is used, for example, the condensation product from 2 mols 4- aminoazobenzene and 1 mol 2:4-dichloroquinazoline.

Similar properties are possessed by the condensation products which are obtained with the aid of further acylation by the agents prescribed in Example 2.

Instead of pyridine there may be used wholly or in part another tertiary amine, for instance dimethylaniline or tripropylamine.

Example 4 7.5 parts of condensation'product from 3 mols aminoazotoluene and 1 mol cyanuric chloride are stirred with 70 parts of pyridine. 11.4 parts of benzoic acid metadisulfochloride are strewn into the mixture and the temperature is allowed to rise to 60 C. and the whole is stirred for about 1 hour at this temperature. The pyridine is then distilled. The residue is taken up with water, the acid liquid is neutralized, if necessary .by means of a weak alkaline agent, for instance sodium triphosphate, and the condensation prod- .uct is salted out, for instance with sodium chloride. After filtering and drying the product is an orange powder which, if desired, may be obtained free from inorganic salts by treatment with methyl alcohol. It dissolves in water to a yellow solution from which the parent pigment may be precipitated by means of algali. The water-soluble product corresponds to probably to one of the two formulas SiOaNa CH3 CE;

in which at least two of the hydrogen atoms linked to the nitrogen atoms are replaced by the atom grouping ZUUAJHLMIMM, uAnouN communes,

parent material one mol of the condensed aminoazotoluene is exchanged'ior ammonia or a primary or secondary organic amine. Such amines are, for example, aliphatic amines, for instance methylamine, allylamine or amylamine,

cycloaliphatic bases, for. instance cyclohexyl-z amine, heterocyclic bases, for instance aminotetrazole or morpholine, aromatic bases, for instance aniline, monomethylaniline, ocor ,8- naphthylamine, a-aminoanthracene, aminocarbazole, aminobenzanthrone, aminopyrene or the like. Similar products are also produced when in the parent material the cyanuric chloride is exchanged for another heterocyclic compound, for instance tribromopyrimidine, dichloroquinazoline, dichlorophenyltriazine. In the last cases obviously only 2 mols of the aminoazo-dyestufi or 1 mol of the aminoazo-dyestufl and 1 mol of ammonia or a primary amine can be condensed. Furthermore, a chloride 01 the sulfobenzoic acid may be exchanged for another acylating agent, for example for naphthoic acid disulfochloride. The formulas probably of such condensation products are for example Search Room Cress Reference Similar products are produced when in the in which at least two of the hydrogen atoms linked to the nitrogen atoms are replaced by the.

atom grouping Example 5 13.3 parts of 2-acetylamin0anthraquinone are stirred with 100 parts of pyridine. Into the mixture are strewn 24 parts of benzoic acid metadisulfochloride and the temperature is allowed to rise to about 80 C. As soon as a sample of the condensation mixture dissolves in water the pyridine is distilled in a vacuum at as low a temperature as possible.

The solid residue which corresponds probably to one of the two following formulas slOsNa C O SOaNa N-O C-CH:

N=CCH| (I) 801M; o=

OsNB

dissolves in water. By addition of alkali the parent pigment can be precipitated from the solution.

A product with similar properties is obtained by using equimolecular quantities of 1- or 2- benzoylaminoanthraquinone or of the condensation product from 1 mol of aminoanthraquinone, 2 mols of aniline and 1 mol of cyanuric chloride instead of Z-acetylaminoanthraquinone.

Example 6 30 parts of the condensation product from 1 mol cyanuric chloride, 2 mols 2-aminoanthraquinone and 1 mol aniline are stirred together with 300 parts of pyridine. Into the mixture are strewn 55 parts of benzoic acid metasulfochloride, and the whole is heated to 100-110 C. As soon as a sample dissolves clearly in water the pyridine is distilled in a vacuum, the residue is dissolved in warm water and the condensation product is salted out, for example with sodium chloride. After filtration, and if desired washing with brine, the product is dried. By extraction with alcohol, for example dry methylalcohol, it may be obtained free from inorganic salts.

The product corresponds-1 probably. to one of the two formulas:

in which at least two of the hydrogen atoms linked to the nitrogen atoms are replaced by the atom grouping S OsNa The new yellowish powder dissolves in water to a feebly yellow solution. By addition of alkali, for example ammonia, or of dilute acid, the parent pigment is precipitated, being insoluble in Water.

This new product is intended forusein dyeing and printing textiles.

Products with like properties and soluble in water may be obtained by treating, for instance, the condensation product from 1 mol cyanuric chloride, 2 mols 1-amino-4-methoxyanthraquinone and 1 mol ammonia with benzoic acid metasulfochloride.

Water-soluble products which may be usedin similar manner for dyeing and printing textiles are produced when in the parent product referred to in the first paragraph of this example the molecule of aniline is exchanged for ammonia or for a primary or secondary amine. Such amines are, for example, aliphatic amines, for example, ethylamine, propylamine, cycloaliphatic bases, for instance cyclohexylamine, heterocyclic bases, for instance aminotetrazole or morpholine, aromatic bases, for instance paratoluidine, monomethylaniline, aor B-naphthylamine, a-aminoanthraquinone, aminocarbazole, 2-aminochrysene, 3-aminopyrene or the like.

The operation remains the: same if in the parent product there is substituted for the'2 mols of Z-aminoanthraquinone another residue capable of being vatted, such as for example aminopyranthrone, aminopyrenequinone or aminodibenzanthrone. If the parent material selected is one of very high molecular weight, it is to be recommended that there shouid be used, as acylating' agent a product with more than one sulfa-group; for example benzoic acid disulfochloride. Final- 1y, condensation. 11110111101782 may also be used'in which instead: on cyanuric: "chloride-otherrhalides:

o1:- heterocyclic: G-ring; systems; for: instance: dis.-

chloroquinazoline; maybe used; 'I'hustheepmd uct' of; the actiorn offbenzoic: acid disulfochioride;

on the condensation product from dici'rloroquinazolinezandi2 mols of fi-anthraquinonehas: the probable formula.

S OaNii C O SOrNasome.

the product of the action of benzoic acid. disulfochloride on the condensation product from 1 mol of aminodibenzanthrone and 2 mols of aniline and 1 mol of cyanuric chloride has the probable formula OiNa in which perhaps one of the atom groupings S 0 ENE E 'QQMPUUND P 1 i1 3 E 2 5Q 2 35 igigm search 2,235,480- 7 of aniline has probably one of the following and formulas:

C0-CHCl-S OSNB N N 3 i e J: NaSOr-CICH- O O-CHCl-S OsNa and Q -i I &

in which at least two of the hydrogen atoms linked to the nitrogen atoms are replaced by the atom grouping Example 7 7.3 parts of the condensation product from 1 mol cyanuric chloride, 1 mol 2-aminoanthraquinone, 1 mol 4-amino-2z1-anthraquinoneacridone and 1 mol aniline are stirred together with about parts of pyridine. 12.8 parts of benzoic acid 3:5-disulfochloride are added. The temperature is raised to 114 C. and the whole is stirred at the boiling temperature until a sample of the mass dissolves in water to a brown solution. 7

As soon as this condition is attained, the Pyridine is distilled at as low a temperature as possible and the procedure follows that described in Example 6.- There is obtained a dark powder which corresponds probably to one of the two following formulas a SO Na l \N SOzNa 6 Y NQCMSQSCMNB O NH I E H N/ \\N n I l- 5-1 in which at least two of the hydrogen atoms linked to the nitrogen atoms are replaced by the atom grouping and which dissolves in water to a brown solution, wherefrom the parent material pigment may be precipitated in the form of green flocks by addition of alkali.

Example 8 SIOaNa CH:N 0

log

dissolves in water to a reddish solution and dyes wool in an acid bath flesh-red. When the aqueous solution of the new condensation product is warmed with caustic alkali, the parent pigment separates after some time.

Example 9 16.4 parts of 1-amino-l-paratoluidoanthraquinone are stirred with parts of pyridine. Into the mixture are strewn 36 parts of toluenedisulfochloride, the temperature is raised to the boiling point and maintained there until a sample of the mass is soluble in water at the said temperature. The pyridine is removed by distillation in a vacuum and the residue may be Room worked up as usual. There is obtained a dark and: powder which corresponds probably to the forin which at least two of the hydrogen atoms linked to the nitrogen atoms are replaced by the atom grouping The procedure is similar with the Parent materials of the preceding examples, for instance by using in this reaction stearoylmethylamide there is obtained a product of one of the probable foran aqueous solution of which dyes wool violet in an acid bath.

Example 10 6 parts of the condensation product from 1 mol cyanuric chloride with 2. mols Z-aminoanthraquinone and 1 mol aniline are heated for 3 hours at 100-110 C. with 9.6 parts of parachloromethylbenzoyl chloride in 60 parts of pyridine after which time a sample of the mass dissolves clearly inwater. The pyridine is then distilled in a vacuum and the product of the reaction isolated by the procedure described in Example 6. It dissolves in water to a yellow solution from which the insoluble parent pigment is precipitated on addition of-dilute alkali. The water-soluble product corresponds probably to one of the formulas and ooomI'-I coOcrn;N-c1 oo 00011:?

! CrzHaa-('J.=NCH1 11 l N I -N-o \CN- t t which constitutesa cation active: textile assistant 4 which in the form of a salt'oi a. strong acid. dis- I solves to a strongly foaming solution. The solu- 0 tions are saponified easily by heating them with a saponifying. agent, the stearoylmethylamide be- NCOOCH:ZNCI ing split on. If this. reaction is. applied to the parent materials resembling dyestufl's used in Ex- I I amplesIi-Q, there are obtained products which in the form of their salts are soluble in water; The

probable formulas of such products are for example fill) bll inilo' n '1, omzoum 'CDMPQUNUS, 2 5

CH C

In these formulas one of the atom groupings is perhaps replaced by one hydrogen atom.

Example 11 8 parts of the product of reaction of benzoic acid sulfochloride on the condensation product from 1 mol cyanuric chloride, 2 mols 2-aminoanthraquinone and 1 mol aniline, 33 parts of water, 54 parts of neutral starch tragacanth thickening and 5 parts of thiodiglyool are worked up to form a printing paste. A cotton fabric is printed with this paste, then dried, steamed in a Mather-Flatt apparatus and developed by passage through a caustic soda solution of 6 per cent. strength at room temperature; by washing and soaping at the boil there is obtained an intense yellow print.

The fixing of the dyestuif, that is to say the splitting off of the acyl-group which lends solubility, may be performed by steaming the printed fabric for 4-5 minutes in a Mather-Flatt apparatus containing formic acid vapor or by handling the printed and steamed fabric for 2-3 minutes in a bath which contains per liter 20 cubic centimeters of sulfuric acid and 25 grams of sodium sulfate, the temperature of this bath being 60-70 C.

In this manner there is obtained a yellow fast print.

What we claim is:

1. Process for the manufacture of new condensation products which comprises causing halides of mono-nuclear aromatic acids which contain simultaneously carboxyl groups and sulfonic groups, to act in the presence of pyridine on 7 compounds of the general formula R -IIIRz] which are free from hydroxyl groups, carboxyl groups and sulfonio groups, and in which n stands for a whole number greaterthan 1 and smaller than 4, R1 stands for the radical of a heterocyclic six-membered system whose heterocyclic sixmembered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic six-membered ring contains at least twice and not more than three times the atom grouping stands for the radical of a primary amine.

2. Process for the manufacture of new condensation products which comprises causing halides of mono-nuclear aromatic acids which contain simultaneously oarboxyl groups and sul: fonic groups, to act in the presence of pyridine on dyestuffs which are free from hydroxyl, carboxyl and sulfonic groups and correspond to the general formula Rl- N-m] stands for the radical of a primary amine, said primary amine being an amino-dyestufi.

3. Process for the manufacture of new con densation products which comprises causing halides of mono-nuclear aromatic acids which contain simultaneously carboxyl groups and sulfonic groups, to act in the presence of pyridine on azo-dyestuffs which are free from hydroxyl, carboxyl and sulfonic groups and correspond to the general formula in which n stands for a whole number greater than 1 and smaller than 4, R1 stands for the radical of a heterocyclic six-membered system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic six-membered ring contains at least twice and not more than three times the atom grouping ('}=N HN-R:

and

IIIR:

stands for the radical of a primary amine, said primary amine being an amino-azo-dyestufi.

4. Process for the manufacture of new condensation products which comprises causing halides of mono-nuclear aromatic acids which contain simultaneously carboxyl groups and sulfonic groups, to act in the presence of pyridine on anthraquinone-dyestuffs which are free from hydroxyl, carboxyl and sulfonic groups and correspond to the general formula in which n stands for a whole number greater than 1 and smaller than 4, R1 stands for the radical of a heterocyclic six-membered system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic six-membered ring contains at least twice and not more than three times the atom grouping (|]=N HN-Rl and 1TIR:

stands for the radical of a primary amine, said primary amine being an amino-anthraquinone-' dyestuif.

5. Process for the manufacture of new condensation products, which comprises causing a chloride or metasulfobenzoic acid to react on the condensation product of the formula using pyridine as reaction medium.

6. The acid amide-like derivatives of the general formula R1- -l]I-RI] LR: n

in which n stands for a whole number greater than 1 and smaller than 4,

and R: stands for an acyl radical containing at least one salt forming group selected from the group consisting of carboxyl groups, sulfonic groups and quaternary ammonium groups, which products are water-soluble powders which, when treated with mild saponifying agents,- regenerate the condensation product free from radicals R3, hydroxyl, carboxyl and sulfonic groups and corresponding to the formula [lg-Rs] n, R1 and R2 having apart from the foregoing statement, the meaning given at the beginning of this claim.

7. The acid amide-like derivatives of the general formula R1 R|1 LR:

in which 1!. stands for a whole number greater than 1 and smaller than 4,

IIIR:

stands for the divalent radical of an amine, said amine. being an amino-dyestufl free from hydroxyl, sultonic and carboxyl groups, R1 stands tor the radical of a. heterocyclic six-membered "batman system whose heterocyclic six-membered ring consists of carbon and nitrogen-atoms or which at least 3 and not more than 2 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic sixmembered ring contains at least twice and at the most three times the atom grouping and R3 stands for an acyl radical containing at least one salt forming group selected from the group consisting of carboxyl groups, sultonic groups and quaternary ammonium groups, which products are water-soluble powders which, when treated with mild saponifying agents. regenerate the dyestufl! free from radicals Ra, hydroxyl, carboxyl and sulfonic groups and corresponding to the formula Rl -NRl] it n, R1 and R2 having, apart from the foregoing statement, the meaning given at the beginning of this claim.

8. The acid amide-like derivatives of the general formula Ka li-'31:] 1

in which n stands for a whole number greater than 1 and smaller than 4,

stands for the divalent radical of an amine, said amine being an amino-azo-dyestufl free from hydroxyl, sulfonic and carboxyl groups, R1 stands for the radical or a heterocyclic six-membered system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms andat least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic sixmembered ring contains at least twice and at the most three times the atom grouping and R3 stands for an acyl radical containing at least one salt forming group selected from the group consisting of carboxyl groups, sulfonic groups and quaternary ammonium groups, which products are water-soluble powders which, when treated with mild saponifying agents, regenerate the azo-dyestufl free from radicals Ra, hydroxyl, carboxyl and sulionic groups and corresponding to the formula m n-11,] Ln

n, R1 and R2 having, apart from the ioresoins statement, the meaning given at the beginning or this claim.

U983 iicicronce 9. The acid amide-like derivatives or the general formula Ri N- RI] in which n stands for a whole number greater than 1 and smaller than 4,

stands for the divalent radical of an amine, said amine being an amino-azo-dyestufl free from hydroxyl, sulionlc and carboxyl groups, R1 stands for the radical of a triazine compound to which the group is linked at a grouping, and Rs stands for an acyl radical containing at least one salt forming group selected from the group consisting of carboxyl groups, sulfonic groups and quaternary ammonium groups, which products are water soluble powders which, when treated with mild saponifying agents, regenerate the azo-dyestufl free from radicals R3, hydroxyl, carboxyl and sulfonic groups and corresponding to the formula n, R1 and R: having, apart from the foregoing statement, the meaning given at the beginning of this claim.

10. The acid amide-like derivatives of the general formula R1-LIIIR|] L In in which n stands for a whole number greater than 1 and smaller than 4,

stands for the divalent radical of an amine, said amine being an amino-anthraquinone-dyestufi which is free from hydroxyl, sulfonic and carboxyl groups, R1 stands for the radical of a heterocyclic six-membered system whose heterocyclic six-membered ring consists of carbon and nitroen atoms or which at least 2 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic six-membered ring contains at least twice and not more than three times the atom grouping C=N I I -RQ 1's and R3 stands for an acyl radical containing at least one salt forming group selected from the group consisting of carboxyl groups, sulfonic groups and quaternary ammonium groups, which products are water-soluble powders which, when treated with mild saponifying agents, regenerate the anthraquinone dyestuff free from radicals R3,

Search Rear hydroxyl, carboxyl and sulionic groups and-corresponding to the formula 12., R1 and R2 having, apart from the foregoing,

statement, the meaning given atthe beginning of this claim.

11. The acid amide-like derivatives of the general formula R1 iII-R!] in which n stands for a whole number greater than 1 and smaller than 4,

stands for the divalent radical of an amine, said amine being an amino-anthraquinone-dyestufi which is free from hydroxyl, sulfonic and carboxyl groups, R1 stands for the radical of a triazine compound to which the Iii-R1 groups is linked at a grouping, and R3 stands for an acyl radical containing at least one salt forming group selected from the group consisting of carboxyl groups, sulfonic groups and quaternary ammonium groups, which products are-water-soluble powders which, when treated with mild saponifying' agents, regenerate the anthraquinone dyestufl' free from radicals R3, hydroxyl, carboxyl and sulfonic groups and corresponding to the formula m n-a1] LH n n, R1 and R2 having, apart from the foregoing statement, the meaning given at the beginning of this claim.

12. The acid amide-like derivatives of the general formula m n-R2] L R3 n in which n stands for a whole number which is greater than one and smaller than 4,

and. R: standsfor an. aoyLra-dical which corresponds to the formula dyestufl which is free from radicals Ra, hydroxyl, carboxyl and sultonic groups and corresponds to the formula Rr-NRl] n, R1 and having apart from the foregoing statement the above given meaning.

13. The acid amide-like derivatives of the general formula R 1N-R2:l

in which n stands for a whole number which is greater than one and smaller than 4,

stands for the divalent radical of an amine, said amine being an amino-anthraquinone-dyestuff which is free from hydroxyl, sulfonic and carboxyl groups, R1 stands for the radical of a heterocyclic six-membered system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms 01' which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic six-membered ring contains at least twice and at the most three times the atom grouping C=N III-R2 R2 and R3 stands for an acyl radical which corresponds to the formula .1: standing for a member of the group consisting of the sulphonic acid radical and alkali metal sulfonate radicals and y for a member of the group consisting of H, the sulphonic acid radical and alkali metal sulfonate radicals, which products arewater-soluble powders, which when treated with miid-saponifyingagents, regenerate the anthraqulnone-dyestufi which is free from radicals grouping and R: stands for an acyl radical which R3, hydroxyl, carboxyl and sulionic groups and corresponds to the formula I|-IRa having apart from the foregoing statement the above given meaning.

14. The acid amide-like derivatives of the general formula Rl I R1] LE3 I in which n stands for a whole number greater than one and smaller than 4,

Il T-R:

stands for the radical of an amine, said amine being an amino-anthraquinone dyestufl which is free from hydroxyl, sulfonic and carboxyl groups, R1 stands for the radical of a triazine compound to which the -NR2 group is linked at a 1L, R1 and corresponds to the formula to the formula R NR|] Li 11, R1 and R2 having, apart from the foregoing statement, the meaning given at the beginning of this claim.

CHARLES GRAENACHER. FRANZ ACKERMANN. HEINRICH BRUENGGER. 

